Ion-exchange resins from a vinyl heterocyclic amino compound and a vinyl-cyclohexene



Patented July 6, 1954 I ION-EXCHANGE RESINS FROM A HETEROCYCLIC AMINOCOMPOUND Y AND A VINYL-CYCLOHEXENIEI ware Gaetano F. 'DAlelio,Pittsburgh, Pa., assignor to Koppers Company, Inc., a corporation ofDela- No Drawing. Application September 24, 1949, Serial No. 117,733

(01. zen-2.1)

22 Claims.

This invention relates to new anion-exchange resins. More particularlyit relates to the prepae ration of anion-exchange resins from vinylpyridines and related compounds.

Ion-exchange resins have been found desirable for a wide variety ofcommercial uses. For example, such resins are being used in thepurification, deionization, and softening of water, the recovery ofmagnesium from sea water and brine, the recovery of copper. and ammoniafrom waste cuprammonium solutions in rayon plants, the recovery of aminoacid from protein hydrolyzates, recovery of certain vitamins fromsolutions, the separation of fission products obtained from uranium andplutonium, the separation of rare earths, the removal of sodium andcopper from oils, the removal of iron and copper from acid liquors,various applications in analytical determinations and in catalyzingesterification, ester hydrolysis, sucrose inversion, etc., and even forthe treatment of eptic ulcers.

Anion-exchange resins used for some of these purposes are disclosed inapplicants U. S. Patent 2,366,008, assigned to the General ElectricCompany, which comprise aminated copolymers of mono-vinyl-aromaticcompounds and divinylaromatic compounds, such as prepared by the 2 posesof this invention the nuclear-substituted alkyl and alkenyl derivativesof vinyl pyridines and vinyl quinolines, as covered by the followingformula, are equivalents of the vinyl pyridines and vinyl quinolines:

CH2=CH R CR wherein R. is hydrogen, alkyl, alkenyl or a divalenthydrocarbon group which forms part of a six-carbon ring by attachment tothe R, on an adjacent carbon atom of the formula, one of the 7 twocarbon atoms which are common to both nitration of an insoluble,.infusible styrenedivinyl benzene copolymer followed by reduction'ficiently satisfactory for many anion-exchange purposes. 7

Anion-exchange resins of great utility have now been found whichcomprise water-insoluble, infusible resins containing the pyridylnucleus, such as prepared from vinyl pyridines and vinyl quinolines andtheir 'alkyl andalkenyl derivatives by cross-linking with cyclic dienecompounds as described more fully hereinafter.

7 The vinyl pyridines and vinyl quinolines which may be used in thepractice of this invention include 2-vinyl-pyridine, 4-vinyl-pyridine,3-vinylpyridine, 2-vinyl-quinoline, 4-vinyl-quinoline, 6-vinyl-quinoline, as well as their alkyl and alkenyl derivatives, e. g.,2-vinyl-4-methyl-pyridine, 2- vinyl-S-methyl-pyridine,3-vinyl-6-methyl-pyridine, 3-vinyl-4-methyl-pyridine,2-vinyl-4,6-dimethyl-pyridine, 2-vinyl-5-ethyl-pyridine, etc. In somecases it may be permissible to use an alpha-methyl-vinyl pyridine whereone of the more active cross-linking agents is used in a highproportion. The inventor has found that for purrings being adjacent tothe N of the formula.

These vinyl pyridines and vinyl quinolines are converted to insoluble,infusible polymers by cross-linking of the vinyl pyridine or vinylquince line molecules by copolymerization with at, least onecopolymerizable cyclic diene hydrocarbon in which the unsaturation iseither in the ring or in both the ring and a side chain comprising avinyl or isopropenyl group: Example of cyclic dienes suitable for thepurposes of this invention are cyclopentadiene, dicyclopentadiene,cyclohexadiene, vinyl cyclohexenes, e.. g., 4-vinyl-cyclohexene (1 vinylcyclohexene 3), 1 vinyl 1-methyl-vinylcyclohexene-3, etc, cyclohexene,e. g., l-(alpha-methyl-vinyl) -4- methyl-cyclohexene-3, etc.

The invention may be best described by the following examples. i Theseexamples serve to illustrate various methods of practicing the inventionand are not intended as limitations to the scope or the invention. Inthese examples and throughout the specification "parts and percent aregiven in parts and percent by weight.

Example I Cross-linked copolymers of z-vinyl-pyridines are made in beadform by suspension polymerization in a pressure-tight autoclave by thefollowing procedure. To the autoclave are added:

0.18 part benzoyl peroxide-dissolved in vinyl 0.03 part sodium oleateisopropenyl The autoclave is then closed and agitated by a rockingmechanism while the autoclave is immersed in a controlled-temperaturebath at 90 C. for about 10 hours and then at 113-115 C. for about hours.The resultant copolymer beads are washed with dilute hydrochloric acidto remove any suspension agent, thenwith dilute sodium hydroxide toremove adsorbed hydrochloric acid, then with water, and subsequentlydried at 70 C. for about two hours.

Example II Ten parts of water-insoluble copolymer beads of Example I arewet with IOU-parts of distilled water, and then 200 parts of standardhydrochloric acid solution are added with shaking. After standing 15minutes the solution is filtered, and the hydrochloric acid remaining inthe filtrate solution is determined by titrating the filtrate withstandard sodium hydroxide solution. The efficiency of the resin isdetermined by cal culating the ratio of chloride ions actually removedirom the solution to the chloride ions theoretically removable. Thesecalculations show that the resin has a high capacity for removingchloride ions from the hydrochloric acid solution.

Example III The exhausted resin from Example II is regenerated bytreating it with approximately N sodium hydroxide solution. Afterfiltering off the sodium hydroxide solution and washing the resin wellwith distilled water, the anion-exchange resin is retested for itsability to adsorb anions according to the method described in Example IIand is found capable of regeneration to a considerable portion of itsoriginalefiiciency.

Example IV Example V A mixture of 90 parts 4-vinylpyridine, and

parts -vinyl-cyclohexene is emulsified by the addition of 180 parts byweight of a10 percent 4 ing agents can be used. Minor portions ofcertain other monomers, such as isobutylene, styrene, chlorostyrene,etc. may be used with the pyridinetype compounds and the cross-linkingagents. However, these other monomers should not have functional groupswhich will interfer with the polymerization activities of the monomersor with the ion-exchange activity of the products, or which may beruptured to give substantial decrease in length of polymer chains or incrosslinking.

Since the basic pyridine or quinoline groups are the active ion-removinggroups in these products,

it is advantageous that the major portion of the polymerization mixturebe of polymerizable monomers containing the pyridine or quinolinenucleus. Instead of starting with a monomer mixture of the pyridine orquinoline compound and the cross-linking agent, it is also'possible toadd the cross-linking agent to partial polymers of the pyridine orquinoline compounds and to effect cross-linking by subsequentlycompleting the polymerization.

The cross-linked copolymers suitable for the practice of this inventioncan'be prepared by any method which will give infusible, insolubleresins, for example by mass, solution, emulsion or suspensionpolymerization. The polymerizations may be advantageously catalyzed byvarious types of catalysts, such as peroxides, e. g., benzoyl, hydrogen,acetyl, acetyl-benzoyl, phthalyl, lauroyl peroxides, tert.-butylhydroperoxide, etc.; and other per-compounds, e. g., ammonium persulfate,sodium ,persulfate, sodium perchlorate, etc.

Anions which may be removed from solution by the insoluble polymers ofthis invention, in addition to the chloride anions mentioned in theexamples, include nitrate ions, sulfate ions, acetate ions, oxalateions, tartrate ions, or any other anions which will react with the basicpyridine or quinoline groups in the resin to form salts. Theseanion-exchange can be readily regenerated by washing with a dilutealkali solution, preferably of an alkali-metal hydroxide which formssoluble salts with the adsorbed anions.

Inert material, such as diatomaceous earth, Alundum, coke, silica,cinders, porous glass, etc.,

- may be .used' as a carrier for the resin in order sodium oleatesolution. After the addition of 0.2

part ammonium persulfate the emulsion is heated to about 36 C. andagitated for about 20 hours. The copolymer powder product obtained afterprecipitation, washing and drying shows anionadsorption and regenerationproperties which compare favorably with the copolymer of Example I.

In the preceding examples the 2- and 4-vinylpyridines and the2-vinyl-quinoline may be replaced by other vinyl pyridines and vinylquinolines, such as mentioned previously, or mixtures comprising anynumber of these compounds. In the place of cyclopentadiene and4-vinyl-cyclohexene, other cyclic diene cross-linking agents or mixturesof any number thereof may be used, such as dicyclopentadiene,cyclohexadiene, etc. as listed hereinbefore. Although the above examplesshow the use of 10 percent crosslinking agent, it will be understoodthat other proportions of such cross-linking agents can be used forpreparing the to increase'the effective surface of the resin forion-exchange. These carriers may be introduced by adding them any timeprior to complete polymerization of the monomers to an infusible,insoluble state. An emulsion ordispersion type of polymerizationisadvantageous for the coating of such carrier materials with the resin.

While thereare above disclosed but a limited number of embodiments ofthe invention, it is possible to produce still other embodiments withoutdeparting from the inventive concept herein disclosed; and it is,therefore, desired that only such limitations be imposed upon theappended claims as are stated therein or required by the prior art.

What is claimed is:

1. An insoluble, infusible resin comprising the polymerization productof polyrn ,Jlfi mass comprising (1) 98-75 percent by Weight of apolymerizable monomer selected from the class consisting of vinylpyridines and vinyl quinolines, and (2) 2-25 percent by weight ofcopolyinerisa'ole vinyl-cyclohexene. 1

2. A water-insoluble resin of claim i, in which the vinyl-cyclohexene is-vinyl-cyclohexene.

3. A water-insoluble resinof claim 1, in which the polymerizable monomeris a vinyl pyridine.

4. A water-insoluble resin of claim 1, in which the polymerizablemonomer is a vinyl quinoline.

5. A water-insoluble resin of claim 1, in which the polymerizablemonomer is a vinyl quinoline and the vinyl-cyclohexene is4-vinyl-cyclohexene.

6. A water-insoluble resin of claim 1, in which the resin is in beadform.

7. A water-insoluble resin of claim 2, in which the resin is in headform.

8. A water-insoluble resin of claim 3, in which the resin is in beadform.

9. A water-insoluble resin of claim 5, in which the resin is in beadform.

10. An inert carrier coated with a water-insoluble resin of claim 1.

11. In a process for the preparation of a waterinsoluble, anion-exchangeresin, the step of polymerizing to an infusible, insoluble resin apolymerizable mass comprising (1) 98-75 percent by weight of apolymerizable monomer from the class consisting of vinyl pyridines andvinyl quinolines, and (2) 2-25 percent by weight of a copolymerizablevinyl-cyclohexene.

12. A process step of claim 11, in which the polymerizable monomer is avinyl pyridine.

13. A process step of claim 11, in which the polymerizable monomer is avinyl quinoline.

14. A process step of claim 11, in which the vinyl-cyclohexene is4-vinyl-cyclohexene.

15. The method of treating liquid media to remove anions therefrom whichcomprises contacting said media with an insoluble, infusible resinprepared from a polymerizable mass comprising (1) 98-75 percent byweight of a polymerizable monomer of the class consisting of vinylpyridines and vinyl quinolines, and (2) 2-25 percent by weight of acopolymerizable vinyl-cyclohexene.

16. The method of claim 15, in which the vinyl-cyclohexene is4-vinyl-cyclohexene.

17. The method of claim 15, in which the polymerizable monomer is avinyl pyridine.

18. The method of claim 15, in which the polymerizable monomer is avinyl quinoline.

19. The method of claim 17, in which the vinyl-cyclohexene is4-vinyl-cyclohexene.

20. The method of treating liquid media to remove anions therefrom whichcomprises contacting said media with an infusible, insoluble copolymerof from 98-75% by weight of 2-vinylpyridine and from 2-25% by weight ofvinylcyclohexene, and separating said copolymer from the liquid media. 7

21. The method of treating liquid media to remove anions therefrom whichcomprises contacting said media with an infusible, insoluble copolymerof from 98-75% by weight of 4-vinylpyridine and from 2-25% by weight ofvinylcyclohexene, and separating said copolymer from the liquid media.

22. The method of treating liquid media to remove anions therefrom whichcomprises contacting said media with an infusible, insoluble copolymerof from 98-75% by weight of 2-vinyl- E-ethyl-pyridine and from 2-25% byweight of vinyl-cyclohexene, and separating said copolymer from theliquid media.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 1,903,500 Calcott Apr. 11, 1933 2,366,008 DAlelio Dec. 26,1944 2,402,020 Cislak June 11, 1946 2,481,810 Barton Sept. 13, 19492,495,147 Street Jan. 17, 1950 2,521,288 Evers Sept. 5, 1950 2,540,984Jackson Feb. 6, 1951 2,581,924 Smith Jan. 8, 1952 FOREIGN PATENTS NumberCountry Date 849,126 France Aug. '7, 1939

1. AN INSOLUBLE, INFUSIBLE RESIN COMPRISING THE POLYMERIZATION PRODUCTOF A POLYMERIZABLE MASS COMPRISING (1) 98-75 PERCENT BY WEIGHT OF APOLYMERIZABLE MONOMER SELECTED FROM THE CLASS CONSISTING OF VINYLPYRIDINES AND VINYL QUINOLINES, AND (2) 2-25 PERCENT BY WEIGHT OF ACOPOLYMERIZABLE VINYL-CYCLOHEXENE.